Yarn treating processes and compositions therefor



Patented Apr. 4, 1939 YARN TREATING PROCESSES AND CG SITIONS THEREFOR Joseph B. Dickey and James G. McNally, Itochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 26, 1937, Serial No. 176,683

22 Claims.

This invention relates to the conditioning of textile yarns and more particularly to the conditioning of filaments and yarns composed of organic derivatives of cellulose such as c llulose acetate, cellulose acetate propionate, cellulose acetate butyrate, etc., to render them more amenable to textile operations such as knitting and the like.

As is well-known in the manufacture of yarns, particularly those composed of or containing cellulose organic derivatives, it is necessary to treat the yarn in order to reduce the tendency toward breakage of the individual filaments or fibers when they are subjectedto various mechanical strains and to lubricate the yarn in order to facilitate handling in such operations as spinning, twisting, winding and reeling. In addition it is necessary to treat yarn to adapt it for use as warp or filling or for the manufacture of various types of knitted fabrics. In knitting, it is particularly important that the yarn be soft and pliable in order that it may conform readily to the contour of the needles and thus produce a closely knit fabric free from such defects as stitch distortion, pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such, as polyhyd-ric alcohols and similar agents as ingredients of yarn conditioning or lubricating formulae, generally in connec tion with mineral, animal or vegetable oils. It has been found, however, that most of the known softening agents and the various formulae containing them have certain drawbacks, one of the most serious of which is high vapor pressure, and in some cases too drastic a solvent action on the yarn. Many of such agents possess slight or insuflicient solvent power for the lubricants with which they are used and it is accordingly necessary to employ blending agents or emulsifying agents in order to obtain operable yarn treating formulae. In addition, many of the known softening and lubricating agents are insufliciently soluble in water to permit satisfactory removal by aqueous scour baths. Y

This invention has as its principal object to provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment of yarns composed of or containing organic derivatives of cellulose and capable of lubricating, softening and rendering such yarns more amenable to knitting and other textile operations. A further and specific object is to provide a class of conditioning agents which augment or assist the lubricating action of various lubricants when applied to such yarns. A still further object is to provide yarn softening and lubricating formulas which can be readily removed from the yarns by the usual scour baths. A still further object is to provide an improved method for the conditioning of yams,. particularly those composed of or containing organic derivatives of cellulose such as cellulose acetate, whereby the yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Still another object is to provide new chemical compounds having the structure and properties discussed below. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in its broader aspects. comprises the discovery that tetrahydrofurfuryl ethers having the general formula:

where R is an alkyl, alkoxyalkyl, hydroxyalkyl, hyd-roxyalkoxyakyl, aralkyl, or aryl group which may be substituted with other groups such as tetrahydrofurfuryl, etc. may be used as yarn conditioning agents and particularly as softening agents with or without the addition of animal, mineral or vegetable oils in the treatment of yarns composed of or containing organic derivatives of cellulose. We have found that these compounds have a slight solvent and/or softening action on cellulose organic derivatives yarns which renders such yarns soft and pliable without at the same time having too drastic a solvent action thereon. As indicated above, included within the broad scope of our invention are the tetrahydrofurfuryl ethers having the general formula:

where R is monoalkoxyalkyl, polyalkoxyalkyl, or the tetrahydrofurfuryl nucleus.

In accordance with the invention these compounds may be applied directly to the yarn during or after spinning, or may be added to the spinning solution itself. We have found that these compounds have exceptional solvent powers which enable them to dissolve mineraloils and blown and unblown, drying and semi-drying vegetable and animal oils and accordingly, and they may be, and preferably are, employed as by Kirner, J. American Chemical Society 52,

3251 (1930). With respect to the preparation of the alkoxy alkyl compounds such as tetrahydrofurfuryl ethoxyethyl ether and tetrahydrofurfuryl methoxymethyl ether, the general meth- 0d of Ashburn, Collett, and Lazell, J. American Chemical Society, 57, 1862 1935) may be modified and used for this purpose. The preparation of typical compounds of this class in accordance with such technique may be carried outas follows: I

Preparation of tetmhyclrofurfuryl ethoxyethyl ether 1 mole of sodium is dissolved in 4 moles tetrahydrofurfuryl alcohol and the solution treated in the cold with 1 mole p-bromoethyl ether. The mixture is stirred 2 hr. at room temperature and 1 hr. on the steam bath to complete the reaction. The precipitated salt is filtered out and the filtrate worked up to give 55 gm. of ether, B. P. -110/17 mm.

Preparation of tetrahydrofarfuryl methoxymethyl ether In similar fashion to above, 1 mole of sodium is dissolved in 4 moles tetrahydrofurfuryl alcohol and treated with 1' mole of chloromethyl ether,'

stirring at 50 for 3 hr. The desired product is obtained as a liquid, B. P. -140/20 mm.-

Preparation of p,p'-tetrahydrofurfuryl ethyl ether 23 gm. (1.0 g. at) sodium are dissolved in 250 cc. tetrahydrofurfuryl alcohol. Then '72 gm. of afi-dichloroethyl ether are added with stirring at a temperature above 50 C. The reactionmixture is heated for 4 hr. at 100 or above. Catalysts such as copper oxide, acetate, copper, etc., may be used. The salt is filtered out and the reaction product distilled. Distillation yields 70- 130 gm. of B,fi-tetrahydrofurfuryl ethyl ether boiling at 213-215/18 mm. a

The above reaction may be run in presence of halogen acid removing compound. In addition to this there is obtained a good yield of a compound having the formula:

boiling at 102-4/8 mm.

Our invention will be more readily understood by reference to the following examples in which the use of tetrahydrofurfuryl ethers as yarn softening agents is described.

Example I.Yarn designed for knitting and composed of cellulose acetate is treated by applying thereto tetrahydrofurfurylmethyl ether by means of an applicatorroll, application being conveniently carried out as the yarn emerges from the spinning cabinet or as it passes from bobbin to bobbin. The amount of the composition applied may run from 4-25% by weight of the yarn.

If the yarn is intended, for weaving, the same general procedure may be followed, except that the amount of the conditioning agent added to the yarn is only about l-5%.

Example II.A conditioning liquid having the following composition: 7

Percent Tetrahydrofurfurylethylether 70 Olive oil 30 applied to cellulose acetate yarn intended for knitting purposes. The amount of the conditioning liquid in this case is from 1-15% and the filaments or fibers thus treated are found to be quite soft and pliable and give improved results in knitting operations.

Other examples of yarn conditioning composition which may be. applied to various types of yarn, particularly those composedof or containing cellulose organic derivatives such as cellulose acetate, cellulose acetate propionate and others'in accordance with our invention and which render such yarn soft and pliable and well-adapted for various textile operations particularly knitting, are the following:

Example III- v Percent Tetrahydrofurfuryl propyl ether 60 Blown olive oil 40 Example IV Percent Tetrahydrofurfuryl butyl ether; 70 Light mineral oil 30 Example V Percent Tetrahydrofurfuryl amyl ether 30 Neats-foot oil 70 Example VI Percent Tetrahydrofurfuryl benzyl ether 20 Blown neats-foot oil 30 Sulfonated olive oil 20 White mineral oil 10 Oleic acid 10 Ethanolamine 3 Water 7 Example VII Percent Tetrahydrofurfurylmethyl ether 20 Sperm oil 60 Laurol 20 Example VIII Percent Tetrahydrofurfuryl ethyl ether 20 Blown sperm oil 30 Sulfonated castor oil 20 Example IX.-A 20% solution of cellulose acetate in acetone in'which is incorporated 1-25% by weight of tetrahydrofurfuryl cetyl ether of the Example X Percent Tetrahydrofurfuryl methyl ether 10 Sulfonated olive oil 5 Gelatin 5 Water 80 Example XI Percent Water Water soluble cellulose ester 5 Tetrahydrofurfuryl' methyl ether 10 Diethylene glycol 5 As indicated above, the alkoxy ethers derivable from tetrahydrofurfuryl alcohol are also particularly valuable as softening and conditioning agents for yarns composed of or containing organic derivatives of cellulose such as cellulose acetate, cellulose acetate propionate, etc. The following examples will further illustrate the use of these compounds:

Example XII.A mixture of 40 parts of tetrahydrofurfuryl-B-ethoxyethyl ether and 60 parts of blown olive oil is applied to cellulose acetate yarn by means of a bath, wick, roll, or spray application. If the yarn is intended for knitting, the amount of the applied compound may run from 4-25% by weight of the yarn. If the yarn is intended for weaving, the amount may vary between 1% and 5% by weight of the yarn. Cellulose acetate filaments or fibers treated in this manner are found to be quite soft and pliable and give improved results in various textile operations such as weaving, knitting, etc.

Other examples of suitable conditioning liquids in accordance with our invention are the follow-i ing:

Example XIII .-A conditioning liquid is made up as follows:

, Percent Tetrahydrofurfuryl oxymethyl ether 70 Olive oil 30 and if the yarn is intended for weaving, the

amount of liquid applied may vary from 1-5% by weight of the yarn.

Example XIV.A conditioning liquid is made up as follows:

Percent ,e-Tetrahydrofurfuryl oxyethyl vinyl ether--- 60 Blown olive oil 40 Example XV Percent 13,5-Ditetrahydrofurfuryloxydiethyl ethe 70 Light mineral oil 30 Example XVI Percent B-Ethoxy-B-ethoxyethyl tetrahydroiurfuryl ether 30 Neats-foot oil "70 Example XVII Percent Tetrahydrofurfuryl-a-glyceryl ether 20 Sperm oil -l 60 Laurol 20 Example XVIII Percent Tetrahydrofurfuryl ethoxyethyl ether 50 Blown sperm oil 30 Sulfonated castor oil 20 Example XIX.'A 20% solution of cellulose acetate in acetone in which is incorporated 1-25% by weight of the cellulose acetate of tetrahydrofurfurylmethoxymethyl ether is extruded through fine orifices into an evaporative atmos- Example XX.--A conditioning liquid is made up as follows:

Percent Water 80 Gelatin 5 Tetrahydrofurfuryl-p-ethoxyethyl ether 10 Sulfonated olive oil 5 Example XXI Percent Water 80 Water soluble cell. ester 5 Tetrahydrofurfuryl p ethoxy p ethoxy ethyl ether Diethylene glycol 5 As will be apparent from the above examples and description, the conditioning agents of our invention may be applied by a wide :ariety of methods. For example, we may e iloy the agent as an ingredient of the spinning mpefrom which the filaments are formed, the amount of the agent so employed depending upon a num ber of factors, such as the particular cellulose derivative used in making the yarn, the solvent or solvent combination used in making up the spinning solution, and the degree of softness or pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, or felt wet therewith or the liquid may be applied by immersion, spray, or otherwise. The particular point at which the liquid is applied may vary. It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the godet or other roll or guide and the point of winding and/or twisting. In some cases, the liquid may even be applied to the yarn after winding onto cones, spools, bobbins, or the like or by the so-called bobbin to bobbin" method. In the case of staple fiber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specific natureof the material to which the agent is applied, the use to which the yarn is eventually. to be put and other factors. For example, in a,

given case where a cellulose organic acid ester yarn, such as a yarn composed of cellulose actate, I

is intended for knitting, about 4 to 25% or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about 1 and 5%.

Although in the above examples we have rev ferred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such as solvents, non-solvents, emulsifylng agents, blending agents and -the like, may be added within the scope of our tions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it is desired to control the solvent or softening action of the conditioning agent, the amount of the agent may be adjusted as, for example, by reducing the amount of the agent and correspondingly increasing the amount of'oil or other ingredient.

While we have described our invention with particular reference to the treatment of yarns composed of organic derivatives of cellulose such as cellulose acetate, the conditioning agents and formulae described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as those composed of or containirig cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

The term yarn as used herein and in the claims is to be understood as including a single.

filament, a plurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture of natural-and artificial filaments or a composite thread formed by twistin together individual strands of natural or art cial materials, as well as cut staple fibers produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditioning agents of our invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor, neats-foot, sperm and other oils. This enables them to be used with any of such oils in making up a variety of yarn treating formulae of varying composition.

The yarn conditioning method and compositions of our invention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especially those composed of or containing organic derivatives of cellulose such as cellulose acetatev and render them soft and pliable and amenable to various textile operations, especially operations such as those involved in weaving and knitting where' complicated designs or stitches are employed, without too drastic an action on the yarn material.

. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of nrineral, animal and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils .when applied to such yarns. In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. By employing the yarn conditioning agents and method of our invention as herein described, one is enabled to obtain highly satisfactory results in the manufacture of yarns and woven fabrics and especially the production from these yarns of closely knit fabrics free from defects such as pin holes, stitch 1. The process of conditioning yarn to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating and softening composition containing a tetrahydrofurfuryl etherhaving the general formula:

o where R is an alkyl, alkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, aralkyl, or aryl group.

2. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating and softening composition containing a tetrahydrofurfuryl ether having the general formula:

( inborn cm CHCH2OR where R is a monoalkoxyalkyl, polyalkoxyalkyl or the tetrahydrofurfuryl nucleus,

3. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing a tetrahydrofurfuryl ether having the general formula:

where R is an alkyl, alkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, aralkyl, or aryl group. 4. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing a tetrahydrofurfuryl ether having the general formula: V

where R is monoalkoxyalkyl, polyalkoxyalkyl, or

the tetrahydrofurfuryl nucleus.

5-. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing a tetrahydrofurfuryl ether having the general formula:

CHi-OH;

where R is an alkyl, alkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, aralkyl, or aryl group and a textile lubricant.

6. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing tetrahydrofurfuryl ethyl ether.

7. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing tetrahydrofurfuryl benzyl ether.

8. A conditioning agent for rendering yarns more amenable to textile operations including knitting, weaving, spinning, and the like which comprises a tetrahydrofurfuryl ether having the general formula:

CH2CH2 Hg CH-CHz-O R where R is an alkyl, alkoxyalkyl, hydroxyalkvl, hydroxyalkoxyalkyl, aralkyl, or aryl group.

9. A conditioning agent for rendering yarns more amenable to textile operations including knitting, weaving, spinning, and the like which hydroxyalkoxvalkyl, aralkyl, or aryl group and a textile lubricating oil.

11. A conditioning agent for rendering textile yarns composed 'of or containing organic derivatives of cellulose more amenable to textile operations including knitting, weaving, spinning, and

the like which comprises a tetrahydrofurfuryl ether having the general formula:

C H: H-C Hr-O R where R is monoalkoxyalkyl, polyalkoxyalkyl, or the tetrahydrofurfuryl nucleus.

12. A conditioning agent for rendering yarns composed of or containing cellulose acetate more amenable to textile operations including knitting, weaving, spinning, and the like, containing tetrahydrofurfuryl ethyl ether.

. 13. A conditioning agent for rendering yarns cbmposed of or containing cellulose acetate more amenable to textile operations including knitting, weaving, spinning, and the like containing tetrahydrofurfuryl benzyl ether.

furiury'l ethers having the formula:

14. 'Ifextile yarn amenable to textile operations including knitting, weaving, spinning and the like impregnated with a lubricant containing a tetrahydrofurfuryl ether having thegeneral formula:

where R is an alkyl, alkoxyalwh hydroxyalkyl', hydroxyalkoxyalkyl, aralkyl, or aryl group.

i5. Textile yarn amenable to textile operations including knitting, 'weaving, spinning, and the like impregnated with a lubricant containing a tetrahydrofurfuryl ether having the general formula:

where R is monoalkoxyalhl, polyalkoxyalkyl, or

the tetrahydrofurfuryl nucleus.

16. Textile yarns composed of or containing cellulose acetate amenable to textile operations including knitting, weaving, spinning, and the.

like, impregnated with a lubricant comprising tetrahydrofurfuryl ethyl ether.

1'7. Textile yarns composed of pr containing cellulose acetate amenable to textile operations including knitting, weaving, spinning and the like, impregnated with a lubricant comprising tetrahydroturfuryl benzyi ether.

18. As new chemical compounds, tetrahydrowhere R is monoalkoxyalkyi, polyalkoxyalkyl, or the tetrahydrofurfuryl nucleus. I

19. As new chemical compounds, alkoxyalkylethers of tetrahydrofurfuryl alcohol selected from the group consisting of tetrahydrofurfuryl meth oxymethyl ether and tetrahydrofurfuryl-p-hydroxyethyl ether. 4

20. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing p,p'-ditetrahydrofurfuryloxydiethyi ether.

21. A conditioning agent for rendering yarns composed of or containing cellulose acetate more amenable to textile operations including knitting,

weaving, spinning and the like containing 3,5- ditetrahydrofurfuryloxydiethyl ether.

22. Textile-yams composed of or containing cellulose acetate amenable to textile operations including knitting, weaving, spinning, and the like, impregnated with a lubricant comprising p,'-ditetrahydrofurfuryloxydiethyl ether.

JAMES G. MCNALLY. JOSEPH B. DICKE'Y. 

